The magnetic and transport properties of (Pr1/3Sm 2/3)2/3A1/3MnO3 (A = Ca, Sr and Ba) compounds, prepared by the citrate-gel route, have been investigated. These compounds are found to crystallize in the orthorhombic structure. Charge ordering transport behaviour is indicated only in the Ca-substituted compound. The Sr- and Ba-substituted compounds show a metal-insulator transition and semiconducting-like behaviour, respectively. The magnetoresistance is highest in the Ba-substituted compound. All three samples show irreversibility in magnetization as a function of temperature in zero-field cooled (ZFC) and field cooled (FC) plots. Non-saturating magnetization, even at 5 K and 4 T field, is observed in Ca- as well Ba-substituted compounds.